CN102712855B - Process for increasing a mole ratio of methyl to phenyl - Google Patents

Process for increasing a mole ratio of methyl to phenyl Download PDF

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Publication number
CN102712855B
CN102712855B CN201180005889.7A CN201180005889A CN102712855B CN 102712855 B CN102712855 B CN 102712855B CN 201180005889 A CN201180005889 A CN 201180005889A CN 102712855 B CN102712855 B CN 102712855B
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raw material
weight
aromatic
methyl
benzene
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CN102712855A (en
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A·内伊兹
E·P·博尔丁格
G·J·加吉达
D·E·伦德
J·E·雷科斯凯
D·E·麦克维克
P·T·巴杰
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Universal Oil Products Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G35/00—Reforming naphtha
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/104—Light gasoline having a boiling range of about 20 - 100 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1096—Aromatics or polyaromatics
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

One exemplary embodiment can be a process for increasing a mole ratio of methyl to phenyl of one or more aromatic compounds in a feed. The process can include reacting an effective amount of one or more aromatic compounds and an effective amount of one or more aromatic methylating agents to form a product having a mole ratio of methyl to phenyl of at least about 0.1:1 greater than the feed.

Description

For improving the method for methyl to the mol ratio of phenyl
right of priority describes
This application claims the right of priority of the U. S. application 12/689,560 that on January 19th, 2010 submits to.
Invention field
The present invention relates generally to the method for the methyl for improving such as one or more aromatic substance to the mol ratio of phenyl.
description of related art
Generally speaking, the feed naphtha that aromatics device can process hydrotreatment produces various product, such as benzene and one or more dimethylbenzene.But, such as, depending on market condition, the aromatic substance of producing higher replacement may be needed.In addition, when producing motor spirit product, more and more stricter legislations of environmental protection may need lower benzene content.Therefore, there is the demand to the alternative method removing benzene from such as gasoline.Thus, allow neatly benzene to be converted into other and more the system and method for high-value product may make us expecting.
But existing method can use may need processing further with the catalyzer of the reactant and/or costliness that are separated undesirable by product.Therefore, the aromatic substance that benzene can be converted into other and replace, the reagent simultaneously undesirable product and/or side reaction being minimized advantageously are provided.
summary of the invention
An exemplary embodiment can be the method for the methyl for improving one or more aromatic substance in raw material to the mol ratio of phenyl.Described method can comprise one or more aromatics methylating reagents reaction of one or more aromatic substance and the significant quantity making significant quantity, forms the product that methyl is the height at least 0.1:1 than raw material to the mol ratio of phenyl.
Another exemplary embodiment can be the method for making one or more aromatic substance react in the feed.Described method can comprise the raw material reaction making to include one or more aromatic substance of effective amount and one or more aromatics methylating reagents of significant quantity, obtains the product relative to the aromatic ring rate of recovery of raw material to be 85-115mol% and methyl to the mol ratio of phenyl the be height at least 0.1:1 than raw material.
Another exemplary embodiment can be the method for the methyl for improving one or more aromatic substance in raw material to the mol ratio of phenyl.Described method can comprise one or more aromatics methylating reagents from stream are provided to the reaction zone being suitable for accepting one or more aromatics methylating reagents, by being increased to than raw material height at least 0.1:1 by the mol ratio of methyl to phenyl, form at least one A7+ compound.
Embodiment disclosed herein can be provided for improving the methyl of one or more aromatic substance to the method for the mol ratio of phenyl.Therefore, aromatic compound conversion can be the compound of higher replacement by method disclosed herein.Depend on market condition, this type of compound transformed can be more high value, such as p-Xylol.Thus, the value of the product produced by aromatics device can be improved.In addition, embodiment disclosed herein can from product as removed the compound of less desirable amount as benzene motor spirit product.
In addition, the aromatic alkylation used or methylating reagent can be one or more non-aromatic compounds or the free radical that can exist in the raw material of petroleum naphtha and can provide from one or more separation column in aromatics device.Thus, non-aromatic compound, such as alkane or naphthenic hydrocarbon, easily can be combined the compound to produce higher replacement with one or more aromatic substance.In addition; usually the compound of lower demand also can be used as the aromatic substance of cumene, indane and other higher replacement, such as, so that their saturated free radical can alkylation or the aromatic substance that methylates, benzene; to produce the product of higher demand, such as dimethylbenzene.Preferably, described method produces other substituting group methyl in one or more aromatic substance.Thus, embodiment disclosed herein can be provided for transforming the economy of benzene in aromatics device and relative simple system.
definition
Term used herein " stream ", " raw material " or " product " can comprise various hydrocarbon molecule, such as straight chain, branching or cyclic alkane, alkene, diolefine and alkynes, and optional other material, such as gas, such as hydrogen, or impurity, such as heavy metal, and sulphur and nitrogen compound.Stream also can comprise aromatic hydrocarbon and non-aromatic hydrocarbons.In addition, described hydrocarbon molecule can be abbreviated as C1, C2, C3 ... Cn, wherein " n " represents that the number of carbon atom in one or more hydrocarbon molecules or abbreviation can be used as the modifier of such as non-aromatic hydrocarbons or compound.Similarly, aromatic substance can be A6, A7, A8 of abbreviation ... An, wherein " n " represents the number of the carbon atom in one or more aromatic molecules.In addition, use together with the abbreviation that subscript "+" or "-" can mark with one or more hydro carbons, such as C3 +or C3 -, it comprises one or more hydro carbons of abbreviation.Such as, abridge " C3 +" refer to that one or more have the hydrocarbon molecule of 3 or more carbon atoms.
Term used herein " district " can refer to the field comprising one or more items of equipment and/or one or more subarea.Items of equipment can comprise one or more reactor or reactor vessel, well heater, interchanger, pipe, pump, compressor and controller.In addition, items of equipment, such as reactor, drying machine or container can comprise one or more district or subarea further.
Term used herein " aromatic alkylation reagent " refers to non-aromatic compound or the free radical of one or more aromatic substance replaced for the production of higher alkyl.The example of one or more non-aromatic compounds can comprise alkane or naphthenic hydrocarbon, preferred at least one C2-C8 alkane or C5 +naphthenic hydrocarbon.Non-aromatic free radical can the finger-type saturated group that becomes the saturated group of the alkyl of straight chain or branching, group of naphthene base or condense with aromatic ring.The aromatic substance with this type of non-aromatic free radical can comprise cumene, indane and tetraline.Alkylaromatic can comprise other substituting group, such as methyl, ethyl, propyl group and higher group.Usually, aromatic alkylation pack carbon containing and hydrogen atom and do not comprise heteroatoms as oxygen, nitrogen, sulphur, phosphorus, fluorine, chlorine and bromine.
Term used herein " aromatics methylating reagent " refers to non-aromatic compound for the production of higher one or more aromatic substance methyl substituted or free radical.The example of one or more non-aromatic compounds can comprise alkane or naphthenic hydrocarbon, preferred at least one C2-C8 alkane or C5 +naphthenic hydrocarbon.Non-aromatic free radical finger-type can become the saturated group of straight chain or branched-alkyl, group of naphthene base, or the saturated group condensed with aromatic ring.The aromatic substance with this type of non-aromatic free radical can comprise cumene, indane and tetraline.The aromatic substance that methylates can comprise other substituting group methyl.Usually, aromatics methylating reagent comprises carbon and hydrogen atom and does not comprise heteroatoms as oxygen, nitrogen, sulphur, phosphorus, fluorine, chlorine, bromine and iodine.This type of heteroatomic compound can be described as " methylating reagent " and can comprise compound as methyl iodide, methyl-sulfate, dimethyl carbonate and three methyl fluorosulfonates.
Term used herein " free radical " refers to part or the group of compound.Thus, exemplary free radical can comprise methyl, ethyl, cyclopropyl, cyclobutyl and the condensed ring group for aromatic ring.
Term used herein " enrichment " can refer to that the amount of a kind of compound or a compounds in stream is for usual at least 50mol%, and preferred at least 70mol%.
The amount that term used herein " substantially " can refer to a kind of compound or a compounds in stream is at least 80mol% usually, preferably at least 90mol%, and at least 99mol% best.
Term used herein " metal " can comprise rhenium, tin, germanium, lead, indium, gallium, zinc, uranium, dysprosium, thallium, chromium, molybdenum, tungsten, iron, cobalt, nickel, platinum, palladium, rhodium, ruthenium, osmium or iridium.
Methyl used herein can calculate as follows to the ratio of phenyl:
Methyl: phenyl mol ratio=[sum of methyl]/[aromatic ring sum]
Wherein:
Aromatic ring sum=all i (MS (i)/MW (i) * NR (i) sum
Sum=all i (MS (i)/MW (i) * ME (the i)) sum of methyl
I: classes of compounds
The molecular weight of material i: MW (i)
Aromatics (benzene) the number of rings order of material i: NR (i)
The number of methyl groups that the phenyl ring of material i connects: ME (i)
The mass content of material i: MS (i) in raw material
Example calculation method for various classes of compounds is described in hereinafter:
Monocyclic aromatics: i: toluene, NR (i)=1, ME (i)=1; I: dimethylbenzene, NR (i)=1, ME (i)=2
Fused aromatic compounds: i: indane, NR (i)=1, ME (i)=0; I: tetraline, NR (i)=1, ME (i)=0;
I: naphthalene, NR (i)=2, ME (i)=0
Substituting group on saturated condensed ring: i:1-methyl-indane and 2-methyl-indane (one of them methyl is connected described five carbocyclic rings), NR (i)=1, ME (i)=0
Substituting group on unsaturated condensed ring: i:4-methyl-indane and 5-methyl-indane (one of them methyl is connected phenyl ring), NR (i)=1, ME (i)=1; I: dimethyl 2,6-naphthalene, NR (i)=2, ME (i)=2
Therefore, then counting when methyl connects aromatic group such as phenyl, then not counting when methyl connection (such as condenses) saturated rings (ring compound for having aromatics and saturated rings) time wholly or in part.
The aromatic ring rate of recovery (mol%) of relative raw material used herein can calculate as follows:
The aromatic ring rate of recovery=[aromatic ring of product sum, in mole]/[the aromatic ring sum of raw material, in mole] * 100%
C6 from raw material used herein +the transformation efficiency (% by weight) of non-aromatic compound can calculate as follows:
Transformation efficiency=((raw material C6 +the total mass of non-aromatic compound)-(product C 6 +the total mass of non-aromatic compound))/(raw material C6 +the total mass of non-aromatic compound)) * 100%
describe in detail
Embodiment provided herein can provide alkyl (preferable methyl) mol ratio to phenyl to be greater than the product of the mol ratio in raw material.Especially, one or more C8 can be comprised -the raw material of hydro carbons can be provided to and can improve methyl substituted reaction zone on aromatic ring.Usually, raw material can be provided by a source or multiple source, and include one or more aromatic substance of effective amount and one or more are without heteroatomic non-aromatic compound or the aromatic substance with saturated group, i.e. one or more aromatic alkylation or methylating reagent.Usually, raw material can from various source, such as following product: reformation, hydrotreatment, catalysis or non-catalytic cracking, extracting is distilled, comprised in such as pygas, oligomerisation, condensation, hydroprocessing, coking, decompression aromatic substance with non-decompression hydrocarbon is separated and arbitrary combination.In addition, liquefied petroleum gas (LPG), the reformate obtained from cracking and from least one in the Raffinate in aromatic substance extracting district can be used from the material combination of originating as mentioned above separately or with at least one.Non-aromatic compound and saturated group can be used as aromatic alkylation (preferable methyl) reagent, to increase the number of alkyl in aromatic substance (preferable methyl).Although provided by embodiment discussed in this article benefit is the number increasing methyl, will also be understood that the number of alkyl also may be enhanced simultaneously.Therefore, aromatics methylating reagent also can be used as aromatic alkylation reagent.
Non-aromatic compound can comprise at least one in one or more naphthenic hydrocarbon and alkane independently, and can form the raw material of at least 5 % by weight.Optionally, one or more non-aromatic compounds also can comprise one or more alkene.Usually, non-aromatic compound comprises at least 2, preferably 3, even more preferably 4 carbon atoms, and can comprise and preferably in ring, have at least 3, expects the naphthenic hydrocarbon of 5 carbon atoms, and, independently, C2-C8 alkane.In other preferred embodiment, non-aromatic compound can comprise one or more C6 +non-aromatic compound.In a further preferred embodiment, one or more C6 +non-aromatic compound can comprise at least one in dimethylcyclopentane and methylcyclopentane.Raw material can comprise one or more naphthenic hydrocarbon of at least 10 % by weight or one or more naphthenic hydrocarbon of 10-70 % by weight, relative to the weight of raw material.In addition, raw material can comprise one or more C2-C5 hydro carbons of at the most 50 % by weight, relative to the weight of raw material.
Generally speaking, raw material also can comprise aromatic substance, such as A6 +.Aromatic substance can comprise benzene, toluene, one or more dimethylbenzene, naphthalene, ethylbenzene and one or more multi-nucleus aromatic compounds.Raw material also can comprise naphthalene nucleus or multiple fused aromatic ring as multi-nucleus aromatic compound (can be abbreviated as " PNA " hereinafter).
In addition, aromatic substance also can comprise saturated group.This compounds can comprise cumene, indane and tetraline.As discussed above, described saturated group can be used as aromatic alkylation (preferable methyl) reagent.
About raw material, raw material comprises 20 % by weight usually, preferably one or more aromatic substance of 35 % by weight.In addition, raw material can comprise the benzene of 5 % by weight, and all the other are non-aromatic compound, and maximum is the toluene of 5 % by weight.In order to obtain the product being rich in dimethylbenzene, in raw material, preferred benzene content is for being less than 75 % by weight, relative to the weight of raw material.In order to obtain the product being rich in toluene, the benzene content in raw material can be and is greater than 75 % by weight, relative to the weight of raw material.In another embodiment, raw material comprises the toluene of at least 5 % by weight and the benzene of at least 5 % by weight usually, and all the other are non-aromatic compound, based on the weight of raw material.In yet another preferred embodiment, raw material comprises the non-aromatic hydrocarbons of the benzene of 0.5-99.5 % by weight, the toluene of 0.5-99.5 % by weight and 0.5-99.5 % by weight usually, based on the weight of raw material.In still another embodiment, raw material can comprise the benzene of at least 20 % by weight, relative to the weight of raw material.
Generally speaking, raw material can comprise one or more aromatic substance of 20-95 % by weight, such as benzene, relative to the weight of raw material.In other embodiments, the benzene content of raw material can be 15-25 % by weight, relative to the weight of raw material.
Usually, raw material is substantially free of containing one or more heteroatomic methylating reagent.Such as, raw material can have and is less than 1 % by weight, is preferably less than one or more methylating reagents of 0.1 % by weight.Substituting, raw material can packet content be at least one or more saturated compounds of 5mol% or the aromatic alkylation reagent of free radical, based on raw material.
Described reaction zone, such as alkyl (preferable methyl) adds district and can operate in liquid phase or gas phase under any suitable condition.Especially, reaction zone can at 250-700 DEG C, the temperature of preferred 350-550 DEG C, 100-21,000kPa, the preferably pressure of 1,900-3,500kPa, 0.1-100hr -1, preferred 2-10hr -1weight hourly space velocity (WHSV), and 0.1:1-5:1, the hydrogen of preferred 0.5:1-4:1: operate under hydrocarbon mol ratio.In the embodiment that another is exemplary, temperature can be at least 460 DEG C, desirably at least 510 DEG C, more desirably at least 560 DEG C, pressure is at the most 7,000kPa, preferably at the most 3,500kPa, and described reaction can carry out the cracking promoting non-aromatic hydrocarbons in the gas phase.Or temperature can be 460-550 DEG C.At higher temperature and lower pressure condition, although do not think bound by theory, believe that non-aromatic hydrocarbons and/or saturated group will form methyl instead of alkyl group.It should be understood, however, that alkylation at least partially may occur, wherein group, as the group of ethyl, propyl group, butyl and Geng Gao, one or more aromatic substance can be replaced.
Any suitable catalyzer such as at least one can be used to comprise the molecular sieve of any suitable material, as aluminosilicate.Catalyzer can include the molecular sieve of effective amount, and it can be has the hole of 10 or more ring memberses containing at least one and can have the zeolite of or higher size (dimension).Generally speaking, the Si/Al of zeolite 2mol ratio for being greater than 10:1, preferred 20:1-60:1.Preferred molecular sieve can comprise BEA, MTW, FAU (comprising zeolite Y and the X zeolite of cubes and form of hexagons), MOR, LTL, ITH, ITW, MEL, FER, TON, MFS, IWW, MFI, EUO, MTT, HEU, CHA, ERI, MWW and LTA.Preferably, zeolite can be MFI and/or MTW.Amount of zeolite suitable in catalyzer can be 1-99 % by weight, preferred 10-90 % by weight.The rest part of catalyzer can be made up of for conveniently manufacturing, providing intensity and the high-temperature-resistant adhesive reduced costs or base material optional.Suitable tackiness agent can comprise inorganic oxide, such as, at least one in aluminum oxide, magnesium oxide, zirconium white, chromic oxide, titanium dioxide, boron oxide, Thorotrast, phosphoric acid salt, zinc oxide and silicon-dioxide.
Usually, catalyzer is substantially free of at least one metal, and generally speaking comprises the total metal content being less than 0.1 % by weight, based on the weight of catalyzer.In addition, catalyzer preferably has and is less than 0.01 % by weight, more preferably has and is less than 0.001 % by weight, have the total metal content being less than 0.0001 % by weight best, based on the weight of catalyzer.
The mol ratio of methyl to phenyl of the product produced from reaction zone can be the height at least 0.1:1 than raw material, is preferably greater than 0.2:1, and is greater than 0.5:1 best.Reaction zone can produce the aromatic ring rate of recovery for general at least 85 % by mole, and preferred 85-115 % by mole, best 99-101 % by mole, relative to raw material.Normally, one or more C6 +the transformation efficiency of non-aromatic compound can be and is greater than 50 % by weight, is preferably greater than 70 % by weight, and is greater than 90 % by weight best.Therefore, one or more C6 +the reaction of non-aromatic compound and benzene can make the benzene amount in final product reduce to minimum.Generally speaking, aromatic substance can accept one or more methyl, and optional other alkyl, such as ethyl, propyl group or higher carbochain substituting group.
Product can comprise one or more A7 +compound, such as toluene, one or more dimethylbenzene and ethylbenzene.So, product can comprise the dimethylbenzene of at least 2 % by weight usually, and preferably 5 % by weight, one or more dimethylbenzene of 10 % by weight best.In addition, the p-Xylol percentage composition in all dimethylbenzene can be at least 20%, and preferably at least 23%, best at least 23.8%.In other preferred embodiment, raw material can comprise the benzene of at least 0.5 % by weight, relative to the weight of raw material, and produces the product with the benzene being less than 0.5 % by weight, relative to the weight of product.In other preferred embodiment, raw material can containing the benzene being greater than 0.5 % by weight, relative to raw material weight and to have benzene be product lower than 20 % by weight, relative to the weight of product.In other preferred embodiment, the benzene content in product can be reduced to and be less than 20 % by weight, is preferably less than 0.5 % by weight, relative to the weight of product.Any benzene existed in raw material can be replaced by the saturated group existed in one or more other aromatic substance are as multi-nucleus aromatic compound, methyl substituted aromatic substance can be rich in obtain, comprise one or more naphthalenes of replacement and the product of other multi-nucleus aromatic compound.
And reaction zone can transform other compound, the compound of such as one or more olefin(e) compounds, one or more sulfur-bearings and one or more halogen-containing compounds.Especially, one or more C3 of 80 % by weight +alkene can be converted, relative to raw material.Preferably, the sulfocompound of at least 95 % by weight, such as thiophene and thiophene derivant, one or more C3 +mercaptan, and one or more heavier halogenide can be converted, relative to raw material.In addition, other compound is as one or more oxygenatedchemicalss, and such as one or more trimethyl carbinol compounds also can be converted.
Normally, Downstream processing can adopt one or more products of embodiment disclosed herein, such as benzene, p-Xylol, m-xylene and o-Xylol.Especially, p-Xylol is once be oxidized the terephthalic acid that can produce for the manufacture of fabric, fiber and resin.In addition, p-Xylol can be used as the clean-out system of steel and silicon wafer, sterilant, coating thinner and in coating and varnish.M-xylene can be used as intermediate to produce softening agent, azoic dyestuff, wood preservative and other this series products.O-Xylol can be used as the raw material producing Tetra hydro Phthalic anhydride.In addition, dimethylbenzene can be used as the solvent in printer, rubber and leather industry usually.In addition, the methyl on dimethylbenzene can be chlorinated as lacquer thinner.Benzene can be used as the raw material preparing hexanaphthene, and the latter can be used to manufacture nylon.Benzene also can be used as the intermediate preparing vinylbenzene, ethylbenzene, cumene and hexanaphthene.In addition, comparatively the benzene of a small amount of can be used for preparing one or more rubber, lubricant, dyestuff, washing composition, medicine, explosive, solidified gasoline and sterilant.
Embodiment
Following examples are used to further illustrate theme embodiment of the present invention.The explanation of these embodiment of the present invention is not mean specific detail claim of the present invention being restricted to these embodiments.These embodiments are the actually operating experiences based on engineering calculation and similar approach.
3 operation all at roughly the same condition Imitating, such as, under the pressure of 2,760kPa, except the 1st is operating as at the temperature of 481.4 DEG C, second operate in the temperature of 511.3 DEG C under, and the 3rd operate in the temperature of 568.5 DEG C under.Composition (% by weight) and the result of raw material and product operation describe in the following table 1:
Table 1
As described above, each product of each operation can have the methyl of at least 0.1:1 higher than raw material: phenyl mol ratio, and the C6-C8 non-aromatic compound transformation efficiency of the product of operation 2 and 3 at average reaction temperature is at least 511 DEG C is more than 90%.
Need not describe in further detail, believe that those skilled in the art can use previous explanation, the present invention is used to greatest extent.Therefore, previous preferred specific embodiments is regarded as only for illustration of, instead of no matter limit rest part disclosed by the invention by any way.
Except as otherwise noted, hereinbefore, all temperature are with centigrade thermometer, and all numbers and percentage ratio are by weight.
From the above description, those skilled in the art can easily determine essential characteristic of the present invention, and, the present invention can be made to carry out various changes and improvements to adapt it to various usages and conditions, and do not depart from its spirit and scope.

Claims (10)

1., for improving the methyl of one or more aromatic substance in raw material to a method for the mol ratio of phenyl, comprising:
A) one or more aromatics methylating reagents comprising at least one in alkane, naphthenic hydrocarbon, alkyl radical and naphthenic hydrocarbon free radical of one or more aromatic substance of significant quantity and significant quantity are made to react in the presence of a catalyst, form the product that methyl is the height at least 0.1:1 than raw material to the mol ratio of phenyl, wherein said catalyzer is one or more catalyzer be selected from BEA, MTW, FAU, MOR, LTL, ITH, ITW, MEL, FER, TON, MFS, IWW, MFI, EUO, MTT, HEU, CHA, ERI, MWW and LTA molecular sieve.
2. method according to claim 1, one or more aromatics methylating reagents wherein said comprise the compound with at least 2 carbon atoms.
3., according to the method for claim 1 or 2, one or more aromatics methylating reagents wherein said comprise at least one in naphthenic hydrocarbon and C2-C8 alkane.
4., according to the method for claim 1 or 2, one or more aromatic substance wherein said comprise benzene.
5., according to the method for claim 1 or 2, one or more aromatic substance wherein said comprise toluene.
6., according to the method for claim 1 or 2, wherein said raw material packet contains the benzene of at least 20 % by weight, relative to the weight of raw material.
7., according to the method for claim 1 or 2, wherein said raw material packet contains the benzene of 20-95 % by weight, relative to the weight of raw material.
8., according to the method for claim 1 or 2, one or more aromatic substance of wherein said significant quantity form at least 20 % by weight, relative to the weight of raw material.
9. method according to claim 1 and 2, wherein said raw material packet contains one or more naphthenic hydrocarbon of at least 10 % by weight, relative to the weight of raw material.
10. method according to claim 1 and 2, wherein said raw material packet contains one or more naphthenic hydrocarbon of 10-70 % by weight, relative to the weight of raw material.
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